EP0010891B1 - Heterocyclisch substituierte Triazolylphosphorverbindungen, sie enthaltende insektizide Zusammensetzungen und Verfahren zur Bekämpfung von Insekten - Google Patents

Heterocyclisch substituierte Triazolylphosphorverbindungen, sie enthaltende insektizide Zusammensetzungen und Verfahren zur Bekämpfung von Insekten Download PDF

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EP0010891B1
EP0010891B1 EP79302206A EP79302206A EP0010891B1 EP 0010891 B1 EP0010891 B1 EP 0010891B1 EP 79302206 A EP79302206 A EP 79302206A EP 79302206 A EP79302206 A EP 79302206A EP 0010891 B1 EP0010891 B1 EP 0010891B1
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triazol
carbon atoms
pyridinyl
phosphorothioate
diethyl
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EP0010891A1 (de
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Chester Emil Pawloski
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Dow Chemical Co
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Dow Chemical Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/72—Nitrogen atoms
    • C07D213/76—Nitrogen atoms to which a second hetero atom is attached
    • C07D213/77—Hydrazine radicals
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having alternatively specified atoms bound to the phosphorus atom and not covered by a single one of groups A01N57/10, A01N57/18, A01N57/26, A01N57/34
    • A01N57/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having alternatively specified atoms bound to the phosphorus atom and not covered by a single one of groups A01N57/10, A01N57/18, A01N57/26, A01N57/34 containing heterocyclic radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6515—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having three nitrogen atoms as the only ring hetero atoms
    • C07F9/6518—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6558—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing at least two different or differently substituted hetero rings neither condensed among themselves nor condensed with a common carbocyclic ring or ring system
    • C07F9/65583—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing at least two different or differently substituted hetero rings neither condensed among themselves nor condensed with a common carbocyclic ring or ring system each of the hetero rings containing nitrogen as ring hetero atom

Definitions

  • This invention is directed to heterocyclic substituted triazolyl phosphorous compounds corresponding to the formula wherein R represents a nitrogen containing heterocyclic radical corresponding to one of the formulae each X independently represents chloro, fluoro, bromo, nitro, alkyl of 1 to 4 carbon atoms, amino, mono- or dialkylamino wherein each alkyl group independently contains from 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, alkylthio of 1 to 4 carbon atoms, alkylsulfinyl of 1 to 4 carbon atoms, alkylsulfonyl of 1 to 4 carbon atoms, cyano, trifluoromethyl, trichloromethyl, phenoxy or substituted phenoxy of the formula wherein each Z independently represents chloro, fluoro, bromo, nitro, cyano, alkoxy of 1 to 4 carbon atoms or alkylthio of 1 to 4 carbon atoms, with the proviso that when either n
  • sterically compatible is employed to designate X and Z substituent groups which are not affected by steric hindrance as defined in "The Condensed Chemical Dictionary," 7th edition, Reinhold Publishing Co. N.Y., page 893 (1966) which definition is as follows:
  • German Offenlegungsschrifts Nos. 2360631 and 2547971 describe certain 1,2,4-triazolylphosphoric acid esters having pesticidal activity.
  • the compounds of the present invention differ from these prior art compounds mainly having regard to the nature of the substituent group R.
  • the compounds of the present invention possess a superior foliar and systemic insecticidal activity and a broader spectrum of activity than the prior art compounds.
  • the triazolyl phosphorous compounds of the present invention possess excellent insecticidal properties and are very useful for the control of insects and for the protection of plants and stored goods from destruction by insects.
  • the phosphorous compounds of the present invention are crystalline solids or liquids which are sparingly soluble in water and which are soluble in most organic solvents.
  • R 2 is C 1 to C 3 alkyl
  • R 3 is C 1 to C 3 alkoxy
  • X is chloro, fluoro, bromo or phenoxy
  • n is 0 or 1
  • R 1 is C, to C 3 alkyl, C 1 to C 2 alkoxy or C 1 to C 2 dialkylamino.
  • the triazolyl phosphorous compounds of the present invention can be prepared by the reaction of an appropriate substituted 3-hydroxytriazole or an alkali metal salt thereof which corresponds to the formula with a phosphoric acid halide corresponding to the formula in the presence of an acid binding agent and a solvent in the above formulae, R, R 1 , R and R 3 are as hereinbefore defined; Me represents sodium, potassium, lithium or cesium and X represents chloro or bromo.
  • the 3-hydroxytriazole reactant or the alkali metal salt thereof, in a solvent is mixed with the phosphoric acid halide and the mixture heated at a temperature of from 20°C up to the boiling point of the specific solvent employed.
  • the reaction can be carried out if desired in the presence of a catalyst.
  • the reaction is usually complete in from 0.1 to 24 hours.
  • the reaction consumes the reactants in stoichiometric proportions, i.e. one equivalent of the 3-hydroxytriazole reactant per equivalent of the phosphoric acid halide and for the most part, these amounts can be employed. It should be noted however, that the actual amount of the reactants to be employed is not critical as some of the desired product is formed when employing any proportions.
  • the alkali metal salt of 3-hydroxytriazole reactant can be prepared by the reaction of molecular equivalent amounts of the 3-hydroxytriazole and an alkali metal hydroxide or carbonate in the presence of a solvent at temperatures of from 20°C up to the reflux temperature of the solvent employed for from 10 minutes to 4 hours. From a practical standpoint, the salt conversion is usually carried out in situ. In addition, it is preferred to employ the alkali metal salt since during the subsequent reaction with the phosphorous acid halide, an insoluble alkali metal halide by-product is formed rather than an acid and no acid binding agent is necessary. Additionally, the insoluble salt can be easily removed allowing for a more convenient product recovery.
  • catalysts useful in carrying out this process include tertiary amines having a pKa of at least 9.5, co-catalysts which are mixtures of quaternary ammonium or phosphonium salts and organic tertiary amines which include quaternary ammonium compounds such as tetraalkylammonium salts, such as tetra-n-butyl-, tetrahexyl-, tri-n-butylmethyl-, cetyltrimethyl-, trioctylmethyl- and tridecylmethyl ammonium chlorides, bromides, bisulfates, tosylates, etc.; aralkylammonium salts, such as tetrabenzylammonium chloride, benzyltrimethyl-, benzyltriethyl-, benzyltributyl-, and phenethyl- trimethylammonium chlorides, bromides, etc.; arylammoni
  • ammonium salts are currently preferred over the phosphonium salts due to cost and commercial availability.
  • the most preferred catalysts are benzyltrimethyl-, benzyltriethyl- tetra-n-butyi and tri-n-butylmethyl ammonium-salts.
  • Suitable tertiary amines include aliphatic trihydrocarbyl amines (e.g. trimethylamine, ethyldimethylamine, butyldimethylamine, N,N,N',N'-tetramethylethylenediamine, and the like); aliphatic heterocyclic amines (e.g. 1,4-diazabicyclo[2.2.2]octane, 1-azabicyclo[2.2.2]octane, 1-methyl-2-imidazoline, 1-methylpyrrolidine, and the like); mixed aliphatic/aromatic amines (e.g. 4-dimethylaminopyridine, 4-(N-pyrrolidion)pyridine phenyldimethylamine, and other like organic, sterically unhindered, nucleophilic, tertiary amines.
  • aliphatic trihydrocarbyl amines e.g. trimethylamine, ethyldimethylamine, butyld
  • suitable diazoles include imidazole, 1-methylimidazole, 1-ethylimidazole, 1-propylimidazole, 1-hexylimidazole pyrazole, 1-methylpyrazole, 1-ethylpyrazole, 1-butylpyrazole, 1-amylpyrazole and 1-hexylpyrazole, and the like.
  • catalysts include a heavy metal or heavy metal salt such as, for example, metallic copper or mercuric chloride.
  • a catalyst it can be added at any stage of the process. In order to achieve the best yield, it is preferred that the catalyst be added at the beginning of the reaction. If, however, the catalyst is a tertiary amine, it is preferred that it be added just prior to the addition of the phosphorous acid chloride.
  • Suitable acid-binding agents are, for example, organic amines such as triethylamine, dimethylaniline, pyridine, inorganic bases such as the hydroxides and carbonates of alkali metals and alkaline earth metals, such as sodium, potassium, calcium, or lithium. These agents are employed in from about about an equimolar amount up to a 10 percent excess based on the triazole reactant.
  • Suitable solvents which can be employed are all the usual organic liquids which are inert under the reaction conditions, for example, acetone, methylethyl ketone, acetonitrile, ethyl acetate, butyl acetate, tetrahydrofuran, dioxane, methylene chloride, carbon tetrachloride, benzene, chlorobenzene, polychlorobenzenes, bromobenzene, dimethylformamide, and xylene.
  • the reaction mixture was cooled and filtered to remove the insoluble by-product and the solvent then removed by evaporation at 50°C under reduced pressure.
  • the oil product which remained was taken up in 250 mls of methylene chloride and then washed twice with 200 mls of water, separated, dried over anhydrous sodium sulfate, filtered and the solvent removed by evaporation under reduced pressure.
  • the crude 0,0 - diethyl - 0 - (1 - (6 - chloro - 2 - pyrazinyl) - 1 H - 1,2,4 - triazol - 3 - yl) phosphorothioate product thus obtained was purified by recrystallization from hexane.
  • Those compounds wherein R 1 is hydrogen can be prepared by the reaction of an appropriate substituted hydrazine carboxamide with excess formic acid or triethyl orthoformate under reflux conditions with or without a solvent being present.
  • Representative solvents include dimethyl sulfoxide, xylene and dimethylformamide.
  • the product is thereafter recovered by cooling the reaction mixture and pouring it over ice and filtering off the solid product which precipitates. Alternatively the reaction mixture is concentrated by distillation and the solid product which precipitates is recovered by filtration.
  • the product regardless of the method of recovery can be further purified by being either washed with a solvent and then dried or washed with water and dried. When water washing is employed it is often advantageous to neutralize the filtrate to recover any product remaining therein.
  • Those compounds where R 1 is chloro are usually prepared by chlorinating the appropriate compound wherein R 1 is hydrogen. This chlorinating step employs a convention chlorinating procedure wherein chlorine gas is bubbled through the triazol-3-ol compound at 100-200C. After the chlorination is complete, the desired product is recovered by filtration.
  • Those compounds wherein R 1 is bromo or fluoro can be prepared by conventional halogen exchange procedures wherein the appropriate triazol-3-ol compound, wherein R 1 is chloro, is treated with potassium bromide or cesium fluoride, respectively. The desired product is then recovered by quenching the reaction mixture with ice and filtering of the solid product.
  • Those compounds wherein R 1 is amino or alkylamino can be prepared by reacting the appropriate triazol-3-ol compound wherein R 1 is chloro, fluoro or bromo with ammonia or an alkylamine in the presence of a solvent such as, for example, dimethyl sulfoxide or isopropylalcohol and at temperatures in the range of about 45° to about 150°C for from 1 to about 3 hours.
  • a solvent such as, for example, dimethyl sulfoxide or isopropylalcohol
  • Those compounds wherein R 1 is alkoxy, alkylthio or phenylthio can be prepared by the reaction of an appropriate triazol-3-ol compound wherein R 1 is chloro, bromo, or fluoro and an appropriate alkali metal alkoxide, alkali metal alkyl- or phenylmercaptide, in the presence of an organic solvent of the type conventionally employed for such reactions.
  • the alkali metal is dissolved in an alcohol corresponding to the alkyl or phenyl group being added.
  • the alkali metal oxy compounds is inherently formed and is employed as such in the following reactions.
  • the mercaptide is formed by adding the appropriate mercaptan to the alcohol solution.
  • To the appropriate above mixture is added the triazol-3-ol reactant and the resulting mixture is refluxed for a time sufficient to complete the reaction, usually from about 1 to about 3 hours.
  • the reaction products are filtered to remove any alkali metal halide, followed by solvent removal by evaporation, distillation or other conventional separatory procedures, leaving the desired product.
  • R 1 is alkylsulfinyl or sulfonyl
  • Those compounds wherein R 1 is alkylsulfinyl or sulfonyl can be prepared by reacting an appropriate triazol-3-ol with an oxidizing agent.
  • the oxidation of any of the alkylthio substituted compounds results, at least partially, in the formation of the corresponding alkylsulfinyl substituted compound.
  • the oxidation of one molecular of the alkylthio substituted compound to the corresponding alkylsulfinyl substituted compound or the oxidation of one molecule of a alkylsulfinyl compound to the corresponding alkylsulfonyl compound requires one atom of oxygen for each sulfur atom oxidized.
  • the oxidation of the alkylthio compound directly to the corresponding alkylsulfonyl compound consumes two atoms of oxygen for each sulfur atom so oxidized.
  • the alkylsulfinyl compounds can be prepared and subjected to continuing oxidative conditions so as to be further oxidized in situ to the corresponding sulfonyl compound. In some instances, depending on the oxidizing agent and process conditions the oxidation proceeds to the sulfonyl compound so rapidly that it is not practical to isolate the sulfinyl compound.
  • Representative oxidizing agents for the production of the sulfinyl compounds include nitric acid and hydrogen peroxide and representative oxidizing agents to be employed in the preparation of the sulfonyl compounds include hydrogen peroxide, and perbenzoic acid.
  • Hydrogen peroxide and conveniently an aqueous solution thereof, can be employed as the oxidizing agent in the production of the sulfinyl and sulfonyl containing derivatives of the present invention.
  • the reaction is carried out in the presence of a liquid reaction medium, such as trifluoroacetic acid, glacial acetic acid or a mixture of acetic acid and acetic anhydride.
  • a liquid reaction medium such as trifluoroacetic acid, glacial acetic acid or a mixture of acetic acid and acetic anhydride.
  • the acid-anhydride mixture is employed as the liquid reaction medium.
  • the reaction takes place at temperatures of from about 75° to about 120°C. In a convenient method, the reaction is carried out at the boiling temperature of the reaction mixture and under reflux.
  • the reactants are contracted in any order or fashion, and preferably in amounts stoichiometric for the preparation of the desired product.
  • the reaction mixture is then maintained at a temperature within the reaction temperature range until the desired degree of conversion is achieved.
  • the sulfinyl or sulfonyl product can be separated by conventional procedures such as evaporation of the reaction medium to obtain the product as a solid residue.
  • the reaction mixture is washed with cold water and is thereafter filtered, centrifuged or the like to obtain the crystalline product.
  • Nitric acid is conveniently employed to oxidize the alkylthio starting material to the corresponding sulfinyl derivative.
  • the reaction can be carried out in the presence of a halocarbon reaction medium such as carbon tetrachloride, methylene dichloride, ethylene dibromide, etc. In a preferred procedure, excess nitric acid is employed as the reaction medium.
  • the reaction proceeds at temperatures between about 15° and about 120°C.
  • the reaction is carried out under reflux conditions at temperatures of from 80° to 120°C and requires only a short period of time for completion, i.e., about 2 to about 7 minutes.
  • the reactants are mixed and the temperature is allowed to rise to the desired temperature and maintained at or about this temperature during the refluxing.
  • chlorine water can also be employed as the oxidizing agent in the preparation of alkylsulfinyl or sulfonyl derivatives from the corresponding alkylthio derivatives.
  • a slurry of the alkylthio containing compound to be oxidized is prepared in water and the slurry agitated while chlorine gas is bubbled in. The mixture is maintained at room temperature until no starting alkylthio material is left unoxidized. If it is desired to convert the sulfinyl compound to the sulfonyl state, the temperature is raised to about 90°C and the mixture maintained at this temperature until oxidation is complete.
  • Those compounds wherein R 1 is alkyl are prepared by the reaction of an appropriate substituted hydrazine carboxamide with an excess of an appropriate triethylorthoester under reflux conditions in the presence or absence of a solvent.
  • Representative solvents include dimethylsulfoxide and xylene. The product is thereafter recovered as set forth hereinbefore for compounds wherein R is hydrogen.
  • Representative ester reactants include compounds corresponding to the formula wherein R 4 is methyl, ethyl or propyl. Specific compounds include triethyl ortho acetate, triethyl ortho propionate and triethyl ortho butyrate.
  • Those compounds wherein R 1 is phenyl can be prepared by the reaction of an appropriate 2-benzoyl-2-(2-pyridinyl)hydrazine carboxamide with an alkali metal hydroxide, at a temperature of from 25° to 75°C for from one minute to one hour, followed by acidifying the reaction product.
  • Those compounds wherein R 1 is methylthiomethyl can be prepared by the reaction of an appropriate triazol-3-ol compound wherein R 1 is chloromethyl with an alkali metal methylmercaptide in the presence of an organic solvent of the type conventionally employed for such reactions under reflux conditions.
  • Those compounds wherein R 1 is hydroxymethyl can be prepared by the reaction of an appropriate triazol-3-ol compound wherein R 1 is chloromethyl with an alkali metal hydroxide in the presence of an organic solvent of the type conventionally employed for such reactions.
  • Those compounds wherein R 1 is thiocyanato can be prepared by the reaction of an appropriate triazol-3-ol compound wherein R 1 is chloro, bromo or fluoro and an appropriate alkali metal thiocyanate under reflux conditions for a time sufficient to complete the reaction, usually from about 1 to about 3 hours.
  • the reaction products are filtered to remove any alkali metal halide, followed by solvent removal by evaporation, distillation or other conventional separatory procedures, leaving the desired product.
  • Those compounds wherein R 1 is chloromethyl or trichloromethyl can be prepared by the selective chlorination of the appropriate compounds wherein R 1 is methyl.
  • chlorine gas is passed into the appropriate triazol-3-ol compound at temperatures of from 20° to 30°C in the presence of a solvent such as carbon tetrachloride for a period of from 30 minutes to 5 hours in the presence of UV light.
  • Those compounds wherein R 1 is trifluoromethyl can be prepared by halogen exchange whereby the appropriate trichloromethyl substituted compound is treated with antimony trifluoride under conventional halogen exchange conditions.
  • a solution was prepared by admixing 17 g (0.10 m) of 2-(6-fluoro-2-pyridinyl)hydrazinecarboxamide and 60 mls of 98 percent formic acid. This mixture was stirred and refluxed for 2 hours and allowed to cool to room temperature. The insolubles were filtered off and dried to produce 3.5 g of the desired 1 - (6 - fluoro - 2 - pyridinyl) - 1 H - 1,2,4 - triazol - 3 - ol which melted at 290°C with decomposition. The excess formic acid in the remaining liquid phase was distilled off under reduced pressure and the solids which precipitated were washed and dried.
  • This product was a second crop of the desired product which also melted at 290°C.
  • the product was recovered in a yield of 60 percent of theoretical and upon analysis, was found to have carbon, hydrogen and nitrogen contents of 46.80, 2.89 and 31.17 percent, respectively, as compared with the theoretical contents of 46.47,2.80 and 31.10 percent, respectively, as calculated for the above named compound.
  • the product melted at 260 0- 262°C and upon analysis was found to have carbon, hydrogen and nitrogen contents of 52.26, 3.90 and 34.79 percent, respectively, as compared with the theoretical contents of 51.89, 3.73 and 34.55 percent, respectively, calculated for the above named compound.
  • a solution was prepared by admixing 17.02 g (0.10 m) of 2-(6-fluoro-2-pyridinyl)hydrazinecarboxamide with 100 ml of triethyl orthoacetate. The mixture was refluxed overnight and the reaction mixture cooled to room temperature and poured over ice water. The solids which precipitated out were recovered by filtration. The solids were washed with methylene chloride and dried under vacuum to yield 11.4 g (58.7 percent of theoretical) of the desired 1 - (6 - fluoro - 2 - pyridinyl) - 5 - methyl - 1H - 1,2,4 - triazol - 3 - ol.
  • a reaction mixture was prepared by suspending 457.6 g (3 m) of 2-pyridinyl-hydrazine carboxamide in 2600 ml of triethylorthoacetate and the mixture refluxed for about 9 hours.
  • the ethanol by-product formed was continuously removed by distillation allowing the reaction temperature to stay at 125°-130°C.
  • the 1 - (2 - pyridinyl) - 5 - methyl - 1H - 1,2,4 - triazol - 3 - ol product was recovered by filtration in a yield of 116 g (66 percent of theoretical) and was washed with chloroform.
  • the white solid which precipitated was recovered by filtration and dried under vacuum to yield 9.5 g (- 70 percent of theoretical) of the desired 1 - (2 - pyridinyl) - 5 - (phenylthio) - 1 H - 1,2,4 - triazol - 3 - ol product.
  • the product melted at 235°-237°C and upon analysis was found to have carbon, hydrogen and nitrogen contents of 55.87,3.79 and 19.90 percent, respectively, as compared with the theoretical contents of 55.91, 3.93 and 20.06 percent, respectively, calculated for the above named compound.
  • a mixture was prepared by admixing 1.84 g (0.00718 m) of 2-benzoyl-2-(2-pyridinyl)hydrazinecarboxamide with 30 ml of 10 percent sodium hydroxide. The mixture was warmed to 50°C to dissolve the carboxamide. The solution was held at 50°C for 10 minutes and the reaction mixture was cooled to room temperature. The reaction product was acidified with 30 ml or 50 percent acetic acid and the white solid which precipitated was recovered by filtration, washed with water and air dried.
  • the 5 - phenyl - 1 - (2 - pyridinyl) - 1 H - 1,2,4 - triazol - 3 - ol product was recovered in a yield of 1.12 g (66 percent of theoretical).
  • the product melted at 240 0- 241 °C and upon analysis was found to have carbon, hydrogen and nitrogen contents of 64.83, 4.35 and 22.46 percent, respectively, as compared with the theoretical contents of 65.53, 4.23 and 23.52.
  • a one liter flask equipped with a dry ice condenser, gas inlet tube, thermometer and a magnetic stirrer was charged with 32.43 g (0.20 m) of 1-(2-pyridinyl)-1 H-1,2,4-triazol-3-ol and 300 ml of water. To this mixture was bubbled 16.3 g (0.23 m) of condensed chlorine gas at 10°-20°C. Thereafter, the reaction mixture was stirred at room temperature for one hour.
  • the substituted hydrazine carboxamide corresponding to the formula wherein R is as hereinabove defined can be prepared by the reaction of an appropriate substituted hydrazino compound of the formula in the presence of a solvent and/or water and a mineral acid with an alkali metal cyanate.
  • the appropriate hydrazino compound in the solvent and/or water is mixed with concentrated mineral acid and the mixture stirred at a temperature of from 20° to 40°C until a clear solution is formed.
  • the alkali metal cyanate is added as an aqueous solution and the mixture stirred at room temperature until the reaction is complete, usually from 1 to 4 hours.
  • the product is thereafter recovered by cooling the reaction mixture and filtering off the solid product which precipitates.
  • the product can be further purified, if desired, by washing with a solvent such as methylene chlorine and/or water and drying.
  • the compounds can be prepared by the reaction of an appropriately substituted haloheterocyclic compound with hydrazine or its hydrate.
  • This reaction can be characterized as follows: wherein X, R and n are as hereinbefore defined, q is chloro, fluoro or bromo and no attempt is made to present a balanced equation.
  • This procedure is especially preferred when preparing compounds wherein the hydrazino group is in a ring position ortho or para to the heterocyclic nitrogen.
  • a solvent such as for example ethanol or isopropanol and a hydrogen halide acceptor
  • Representative hydrogen halide acceptors include, triethylamine, pyridine, or other such conventional material.
  • a large excess of hydrazine can be employed which then acts as a reactant and as the hydrogen halide acceptor.
  • the mixture is maintained under reflux conditions for from 1 to 8 hours.
  • about two-thirds of the solvent is distilled off and the remaining mixture cooled, diluted with water, extracted with a solvent such as methylene chloride and the extracts dried.
  • the insolubles are filtered off and the solvent removed by evaporation under reduced pressure leaving the desired product.
  • the above reactants can be placed into sealed reaction vessel and stirred for from 2 to 16 hours or more at a temperature of from 100° to 150°C, or more, depending upon the reactants.
  • the reaction mixture is cooled and the solid product which precipitates are recovered by filtration and washed with water and methylene chloride, filtered off and dried.
  • one molar equivalent of the appropriately substituted meta-amino compound is mixed with concentrated hydrochloric acid and cooled to 0 to -10°C while a slight (",10 to 2096) excess of the alkali metal nitrate reactant in water is added at a rate to maintain the reaction temperature at below 0°C.
  • This mixture is thereafter slowly added to a fresh solution of stannous chloride in concentrated hydrochloric acid at a rate to maintain the reaction temperature below 0°C.
  • the mixture is stirred for from 1 to 3 hours and the solution made basic.
  • the mixture is extracted with a solvent such as methylene chloride and the extract dried filtered and distilled to recover the crude product.
  • the crude product is purified by dissolving in dilute hydrochloric acid and extracting with methylene chloride.
  • the aqueous phase is made basic and the desired product which precipitates is recovered by filtration, water washed and dried.
  • a solution was prepared by admixing 55 g (0.43 m) of 2-hydrazino-6-fluoropyridine in 240 ml of water with 40 g of concentrated hydrochloric acid in 60 ml of water. The mixture was stirred at 35°C until a clear solution formed. To this reaction mixture was added 37 g (0.46 m) of potassium cyanate in 100 ml of water. After the addition was completed, the reaction mixture was stirred for 2 1/2 hours at room temperature and then cooled to 10°C on an ice bath. The 2-(6-fluoro-2-pyridinyl)hydrazinecarboxamide product was isolated by filtration and washed with methylene chloride in quantitative yield.
  • a solution was prepared by admixing 43 g (0.20 m) of 2-hydrazino-2,3,5-trichlo ' ropyridine in 100 ml of dimethylformamide with 20 g of concentrated hydrochloric acid in 250 ml of water. The mixture was stirred at 35°C until a clear solution formed. To this reaction mixture was added 17 g (0.20 m) of potassium cyanate in 80 ml of water. After the addition was completed, the reaction mixture was stirred for 3 hours at room temperature and then cooled to 10°C on an ice bath.
  • a mixture was prepared by admixing 15.22 g (0.1 mole) of 2-(2-pyridinyl)hydrazinecarboxamide with a solution of 16.2 g (0.16 m) of triethylamine in 200 ml of acetonitrile. The mixture was stirred while a solution of 21.08 g (0.15 m) of benzoyl chloride in 50 ml of acetonitrile was added. After an induction period of N 5 minutes, the mixture exothermed reaching a peak temperature of 52 °C after 10 minutes. The reaction mixture was then stirred, without heating, for 5 1/2 hours and then heated under reflux for 2 hours.
  • the new triazolyl phosphates of the present invention possess excellent insecticidal and acaracidal properties and are very suitable for the control of chewing and sucking insects for the protection of plants and stored goods.
  • the compounds penetrate into the tissues of plants and are highly effective as contact and stomach poison insecticides. Owing to their low toxicity to warm- blooded animals, they are also suitable for the control of ecto and endo-parasites on and in animals.
  • the compounds of the present invention can be employed for the control of one or more of the following arthropods, among others, and their various stages of development (larvae and eggs): insects of the families Muscidae and Culicidae, house flies (Musca domestica), stable flies (Stomoxys calcitrans) and mosquitoes (e.g. Aedes Aegypti, Culex fatigans, Anopheles stephensi7; against insects of the families Curculonidae, Bruchidae, Dermestidae, Tenebrionidae and Chrysomelidae, e.g.
  • green peach aphids Myzus persicae
  • Pseudococcidae e.g. citrus mealybugs (Planococcus citri)
  • Locustidae e.g. migratory locusts (Locusta migratoria)
  • arachnids including the families Acaridae, Ixodidae, Tetranychidae and Argasidae.
  • an insecticidal amount of the phosphorous compound per se or a composition incorporating an insecticidal amount of the compound is used as the toxicant for contact with the pest insect or its habitat.
  • the insecticidal amount is that quantity which elicits toxic mortality among the treated pests.
  • such insecticidal response results by contacting the target pests or their habitat with a composition containing from 0.00001 to 99 or more percent of the active compound in the total composition. Good results are achieved upon contact with a composition containing about 1000 parts of the active compound per million by weight.
  • Suitable compositions include those which are in the form of liquid solutions, liquid emulsifiable concentrates, and dust or granular preparations. Such can be further diluted as and where appropriate with convention diluents.
  • Liquid compositions containing the active compound are prepared by dissolving the active compound in a suitable inert organic solvent such as acetone, toluene, xylene, methylene chloride, chlorobenzene, ethyl ether or petroleum distillates or by dispersing the active compound in water with or without the aid of a suitable surface acting dispersing agent such as can be provided by ionic or nonionic dispersing and emulsifying agents.
  • a suitable inert organic solvent such as acetone, toluene, xylene, methylene chloride, chlorobenzene, ethyl ether or petroleum distillates
  • a suitable surface acting dispersing agent such as can be provided by ionic or nonionic dispersing and emulsifying agents.
  • the aqueous compositions may contain one or more water-immiscible solvents for the toxicants.
  • the carrier comprises an aqueous emulsion, that is, a mixture of water-immiscible solvent, emulsifying agent and water.
  • aqueous emulsion that is, a mixture of water-immiscible solvent, emulsifying agent and water.
  • Dispersing and emulsifying agents which may be employed in the compositions include the condensation products of alkylene oxides with phenols and organic acids, alkylarylsulfonates, polyoxyethylene derivatives or sorbitan esters, complex ether alcohols, mahogany soaps, and the like.
  • the surface active agents are usually employed in the amount of from 1 to 20 percent by weight of the combined weight of the surface active agent and the active compound.
  • the active compound is dispersed in and on a finely divided inert solid such as talcum, chalk, gypsum, and the like.
  • the carriers are mechanically ground with the compounds or wet with a volatile organic solvent solution thereof.
  • dust compositions containing the compound may be prepared from bentonite, fuller's earth, attapulgite, and other clays.
  • these dust compositions may be employed as concentrates and subsequently diluted with additional solid surface acting dispersing agent or with talc, chalk, or gypsum and the like to obtain a desired amount of active agent in a composition adapted to be applied for insect control.
  • such concentrate dust compositions may be dispersed in water with or without the aid of a dispersing agent to form spray mixtures.
  • Granular formulations are conveniently prepared by impregnations, such as through simple mechanical mixing, of the active compound in a presized carrier, usually of the type hereinbefore set forth.
  • the active compound is distributed so as to provide contact of the target insect with toxic amounts of the active compound.
  • Such contact can be achieved through direct contact of the active compound with the target insect or by more indirect means such as by application to its food and/or habitat.
  • the active compound hereof or a composition thereof can be spread throughout the environs of the target host so as to both provide direct and indirect contact thereof or bait compositions incorporating a toxic amount of the active compound or composition thereof can be readily prepared and strategically located so as to provide ultimate contact of the host species therewith.
  • 1 Part of one of the compounds numbered 8, 1 or 20 is mixed with 99 parts of purified kerosene to obtain an oil preparation having an active ingredient concentration of 1 percent.
  • the composition can be atomized or sprayed as is.
  • compositions may be further diluted in their concentrate state and/or dispersed in water to prepare aqueous compositions which have desirable wetting and penetrating properties.
  • These compositions are adapted to be employed to treat target insect life and thus distribute the active compounds to provide contact of such insect life in insecticidal concentrations.
  • Paper cylindrical cartons about 3-5/8 inches (9.2 cms) in diameter by 3-1/4 inches (8.26 cms) high were fitted with wire screen on the top and bottom.
  • Into each cage were placed 6 German cockroaches (Blattella germanica).
  • additional cockroaches were sprayed with a solvent-water-surfactant mixture containing no active toxicant to serve as controls.
  • An aqueous dispersion was prepared by dispersing a predetermined amount of one of the test compounds, which had been dissolved in a suitable inert solvent, and a predetermined amount of a surfactant in a predetermined amount of water.
  • a water-surfactant-solvent mixture containing none of the compounds was also prepared to serve as a control.
  • Sheets containing egg masses of codling moths were pinned to apples and the egg sheets and apples were drenched with an aqueous dispersion of one of the hereinafter set forth compounds. Separate egg masses and apples were also treated with the control mixture. The egg masses/apples were incubated under conditions conducive to the hatching of the eggs and the growth of the larvae therefrom. Ten days after treatment, the apples were examined for the presence of egg hatch and larvae. Counts of the number of larval penetration in the treated fruit were compared to the number present in the untreated control to determine the percent control obtained with the test compounds.
  • This examination determined the minimum concentration in parts of the active compound per million parts of the ultimate dispersion necessary to give at least a 70 percent kill and control of codling moth larvae and/or eggs and the results of this examination are set forth in Table III.
  • aqueous dispersions were prepared by admixing one of the hereinafter set forth compounds, dissolved in a suitable inert solvent, with a predetermined quantity of water and a predetermined amount of a surfactant to give aqueous dispersions containing varying predetermined amounts of one of the compounds as the sole active toxicant.
  • Separate cotton plant leaves were thoroughly wetted by briefly dipping into one of the dispersions and the wetted leaves placed in an open petri dish and permitted to dry. After the leaves were dry, 5 live beet armyworm larvae, approximately late 2nd instar were placed in each petri dish.
  • aqueous dispersions were prepared by admixing one of the hereinafter set forth compounds, dissolved in a suitable inert solvent, with a predetermined quantity of water and a predetermined amount of a surfactant to give aqueous dispersions of varying predetermined amounts of one of the compounds as the sole active toxicant.
  • Separate 3 inch discs cut from tobacco plant leaves were thoroughly wetted by briefly dipping into one of the dispersions and the wetted leaves placed in an open petri dish and permitted to dry. After the leaves were dry, 5 live tobacco budworm larvae, approximately late 2nd instar were placed in each petri dish.
  • Aqueous dispersions were prepared by admixing one of the hereinafter set forth compounds, dissolved in a suitable inert solvent with a predetermined quantity of water and a predetermined amount of a surfactant to give aqueous dispersions containing varying predetermined amounts of one of the compounds as the sole toxicant.
  • Separate chili pepper plants were infested with 20 green peach aphids and the plants sprayed with one of the dispersions to run off.
  • 20 green peach aphids were placed on control plants and the,plants sprayed to run off with a solution containing only water and surfactant. The plants were maintained under conditions conducive to the growth of the plants and aphids.
  • Aqueous dispersions were prepared by admixing one of the hereinafter set forth compounds, dissolved in a suitable inert solvent, with a predetermined quantity of water and a predetermined amount of a surfactant to give aqueous dispersions containing varying predetermined amounts of one of the compounds as the sole toxicant.
  • Separate cotton plants were infested with 20 two spotted spider mites and the plants sprayed with one of the dispersions to run off.
  • 20 two spotted spider mites were placed on control plants and the plants sprayed to run off with a solution containing only water and surfactant. The plants were maintained under conditions conducive to the growth of the plants and mites.

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Claims (19)

1. Verbindung mit der allgemeinen Formel:
Figure imgb0064
worin R einen Stickstoff enthaltenden heterocyclischen Rest bedeutet, der einer von den folgenden Formeln entspricht:
Figure imgb0065
Dabei bedeutet jedes X für sich Chlor, Fluor, Brom, eine Nitrogruppe, eine Alkylgruppe mit 1 bis 4 Kohlenstoffatomen, eine Amino-, Mono- oder Dialkylaminogruppe, worin jede Alkylgruppe unabhängig 1 bis 4 Kohlenstoffatome enthält, eine Alkoxygruppe mit 1 bis 4 Kohlenstoffatomen, eine Alkylthiogruppe mit 1 bis 4 Kohlenstoffatomen, eine Alkylsulfinylgruppe mit 1 bis 4 Kohlenstoffatomen, eine Alkylsulfonylgruppe mit 1 bis 4 Kohlenstoffatomen, eine Cyanogruppe, eine Trifluormethylgruppe, eine Trichlormethylgruppe, eine Phenoxy- oder substituierte Phenoxygruppe mit der Formel:
Figure imgb0066
worin jedes Z für sich bedeutet Chlor, Fluor, Brom, eine Nitrogruppe, eine Cyanogruppe, eine Alkoxygruppe mit 1 bis 4 Kohlenstoffatomen oder eine Alkylthiogruppe mit 1 bis 4 Kohlenstoffatomen, mit dem Vorbehalt, daß wenn ein n 2 oder 3 ist, alle X-Gruppen sterisch ungehindert zueinander sind und alle Z-Gruppen sterisch ungehindert zueinander sind; und n kann unabhängig bedeuten O oder eine ganze Zahl von 1 bis einschließlich 3; R1 bedeutet Hydrogen, Chlor, Fluor, Brom, eine Alkylgruppe mit 1 bis 4 Kohlenstoffatomen, eine Cycloalkylgruppe mit 3 bis 6 Kohlenstoffatomen, eine Phenylgruppe, eine Phenylthiogruppe, eine Alkoxygruppe mit 1 bis 4 Kohlenstoffatomen, eine Alkylthiogruppe mit 1 bis 4 Kohlenstoffatomen, eine Alkylsulfinylgruppe mit 1 bis 4 Kohlenstoffatomen, eine Alkylsulfonylgruppe mit 1 bis 4 Kohlenstoffatomen, eine Thiocyanatgruppe, eine Trifluormethylgruppe, eine Trichlormethylgruppe, eine Aminogruppe, eine Mono- oder Dialkylaminogruppe, worin jede Alkylgruppe unabhängig 1 bis 4 Kohlenstoffatome enthält; R2 bedeutet eine Methylgruppe, eine Athylgruppe, eine Propyl-oder Isobutylgruppe und R3 bedeutet eine Methoxygruppe, eine Athoxygruppe, eine Propoxygruppe, eine Äthylgruppe, eine Mono- oder Dialkylaminogruppe, worin jede Alkylgruppe unabhängig 1 bis 4 Kohlenstoffatome enthält, eine Alkylthiogruppe mit 1 bis 4 Kohlenstoffatomen oder eine Phenylgruppe.
2. Verbindung nach Anspruch 1, worin der heterocyclische Rest ist:
Figure imgb0067
3. Verbindung nach Anspruch 1 oder 2, worin R2 eine Methyl- oder Äthylgruppe ist und R3 eine Methoxy- oder Athoxygruppe.
4. O,O-Diäthyl-O-(1-(6-chlor-2-pyridinyl)-1 H-1,2,4-triazol-3-yl)-thiophosphorsäureester
5. O,O-Diäthyl-O-( 1-(2-pyridinyl)-1 H-1,2,4-triazol-3-yl)-th iophosphorsäureester.
6. O,O-Diäthyl-O-( 1-(6-fluor-2-pyridinyl)-1 H-1,2,4-triazol-3-yl)-thiophosphorsäureester.
7. O,O-Diäthyl-O-( 1-(2-pyridinyl)-5-methyl-1 H-1,2,4-triazol-3-yl)-thiophosphorsäureester.
8. O,O-Diäthyl-O-( 1-(6-fluor-2-pyridinyl)-5-methyl-1 H-1,2,4-triazol-3-yl)-thiophosphorsäureester.
9. O,O-Diäthyl-O-(1-(2-pyridinyl)-5-äthyl-1 H-1,2,4-triazol-3-yl)-thiophosphorsäureester.
10. O,O-Diäthyl-O-( 1-(6-phenoxy-2-pyridinyl)-1 H-1,2,4-triazol-3-yl)-thiophosporsäureester.
11. 0,0 - Diäthyl - 0 - (1 - (6 - phenoxy - 2 - pyridinyl) - 5 - methyl - 1 H - 1,2,4 - triazol - 3 - yl)-thiophosphorsäureester.
12. O,O-Dimethyl-O-(1-(2-pyridinyl)-5-methyl-1H-1,2,4-triazol-3-yl)-thiophosphorsäureester.
13. 0,0 - Diäthyl - 0 - (1 - (2 - pyridinyl) - 5 - (1 - methyläthyl) - 1 H - 1,2,4 - triazol - 3 - yl)-thiophosphorsäureester.
14. O,O-Dimethyl-O-(1-(2-pyridinyl)-1H-1,2,4-triazol-3-yl)-thiophosphorsäureester.
15. Verbindung nach Anspruch 1, worin der heterocyclische Rest ist:
Figure imgb0068
16. 0,0 - Diäthyl - 0 - (1 - (5 - brom - 2 - pyrimidinyl) - 5 - methyl - 1 H - 1,2,4 - triazol - 3 - yl)-thiophosphorsäureester.
17. O,O-Diäthyl-O-(1-(5-brom-2-pyrimidinyl)-1H-1,2,4-triazol-3-yl)-thiophosphorsaureester.
18. Insektizidzusammensetzung, die einen inerten Träger in inniger Beimischung mit einer insektizid wirkenden Menge an einer aktiven Verbindung aus einem der Ansprüche 1 bis 17 enthält.
19. Verfahren zum Töten und/oder Kontrollieren von Insekten, dadurch gekennzeichnet, daß die Insekten oder ihr Verbreitungsgebiet mit einer Zusammensetzung, die als aktiven Bestandteil eine insektizid wirkende Menge einer aktiven Verbindung nach einem der Ansprüche 1 bis 17 enthält, in Berührung gebracht werden.
EP79302206A 1978-10-13 1979-10-12 Heterocyclisch substituierte Triazolylphosphorverbindungen, sie enthaltende insektizide Zusammensetzungen und Verfahren zur Bekämpfung von Insekten Expired EP0010891B1 (de)

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